Hydroxyaryl adducts of decachloro-pentacyclo(5.3.0.0.2,6.04,10.05,9)dcane-3-one and esters thereof

ABSTRACT

HYDROXYAROMATIC DERIVATIVES OF DECACHLOROPENTACYCLO (5.3.0.0,6.04,10.05,9)DECANE-3-ONE (C10CL10O), METHODS FOR THEIR PRODUCTION, AND THE REACTION PRODUCTS OF SUCH DERIVATIVES WITH CARBOXYLIC COMPOUNDS. THESE COMPOUNDS ARE USEFUL AS RESIN INTERMEDIATES TO PREPARED POLYESTERS WHICH CAN BE FURTHER REACTED TO PRODUCE THERMOSETTING PLASTICS. ADDITIONALLY, THESE COMPOUNDS ARE USEFUL AS CROSS-LINKING AGENTS FOR VINYL MONOMERS.

United States Patent Office Patented June 11,, 1974 Int. Cl. C07c 39/12US. Cl. 260-619 D 6 Claims ABSTRACT OF THE DISCLOSURE Hydroxyaromaticderivatives of decachloropentacyclo (5.3.0.0 .0 .0 )decane-3-one (C ClO), methods for their production, and the reaction products of suchderivatives with carboxylic compounds.

These compounds are useful as resin intermediates to prepare polyesterswhich can be further reacted to produce thermosetting plastics.Additionally, these compounds are useful as cross-linking agents forvinyl monomers.

This application is a continuation of application Ser. No, 592,719,filed Nov. 8, 1966, now' abandoned, which is a continuation-in-part ofapplication Ser. No. 191,703, filed May 2, 1962, now abandoned.

The present invention is concerned with new compositions of matter andto processes for their production.

More specifically, this invention relates to hydroxyaromatic derivativesof decachloropentacyclo saturated aliphatic acid such as methacrylic,acrylic or their acid chlorides, unsaturated esters are produced whichcan be transformed to plastic materials by reaction of said esters withfree radical generating catalysts such as benzoyl peroxide, methyl ethylketone peroxide, and the like.

The compounds of this invention also find utility as cross-linkingagents for vinyl monomers, from which thermosetting plastics can beproduced with enhanced thermal properties and fire resistance. Inaddition, the compounds of the instant invention are useful as additivesto conventional polyesters derived fromphthalic and maleic aciddiolsystems.

It is an object of this invention to produce aromatic derivatives ofdecachloropentacyclo(5.3.0.0 .0 .0 decane-3-one.

Still another object of this invention is to utilize such aromaticderivatives in the preparation of novel intermediates for use in polymermanufacturing.

A further object is the production of carboxylic acid derivatives of thearomatic derivatives of decachloropentacycle (5 .3.0.0 .0 .0decane-B-one.

These and other objects of the present invention will become moreobvious from a consideration of the following detailed specification.

Decachloropentacyclo(5.3.0.'0 .0 .0 decane-3-one, formerly known asdecachlorotetrahydro-4,7-methanoindenone, has the formula C Cl O andpossesses the box ketone structure as follows:

c] Cl Cl Cl Cl The aromatic derivatives of the present invention can beprepared by reacting an aromatic hydroxyl compound having at least oneortho or para position available for reaction, withdecachloropentacyclo(5.3.0.0 .0 .0 decane-3-one in the presence of asuitable catalyst. The para positioned reaction product normally is of ahigher melting point than the corresponding ortho product. Thetemperature is preferably in the range between about 50 degreescentigrade and 200 degrees centigrade, although higher and lowertemperatures can be used such as about 0 degrees centigrade to 225degrees centigrade. The reaction is usually complete in a period ofbetween about one hour and. about three hours. The aromatic hydroxylcompound functions as a solvent as well as a reactant in the process. v

The compositions of this invention are presumably prepared by thefollowing equation, although I do not wishto be limited by theory:

catalyst CmClmO-l-ANOH). CmCllo(OH)At(OH).

wherein x is an integer of 1 to 30, and more preferably 1 to about 6, yis an integer from 1 to 30, and more preferably 1 to about 6, and z isan integer from 1 to 6.

The composition of the present invention is represented by the formula:

[( )z ']y( 1o 10 )x wherein x is an integer of 1 to about 6, y is aninteger of 1 to about 6, z is an integer of l to 6, Ar is aryl of 6 toabout 24 carbon atoms and R is independently selected from the groupconsisting of hydrogen and acyl of 1 to about 10 carbon atoms. Ar isaryl or substituted aryl.

Substituents on the aromatic ring may be H, F, Cl, Br or a suitablesubstituent selected from the following:

(a) Alkyl groups of 1 to 18 carbon atoms in" any of their isomeric formsand substituted on the phenolic nucleus in the ortho, meta or parapositions;

(b) Alicyclic groups of 5 to 18 carbon atoms such as cyclohexyl,cyclopentyl, methylcyclohcxyl, butylcyclohexyl, and the like;

(c) Aromatic or aralkyl groups of6 to 18 carbon atoms such as phenyl,alpha-methylbenzyl, benzyl, cumyl, and the like;

(d) Alkyl, alicyclic, aryl and aralkyl ketones wherein the hydrocarbonis as described hereinbefore;

3 (e) Alkyl, alicyclic, aryl and aralkyl carboxylic groups wherein thehydrocarbon is as described hereinbefore; (f) Alkyl, alicyclic, aryl andaralkyl ethers wherein the hydrocarbon is as described hereinbefore.

The substituents on the aromatic ring, including the hydroxyl groups,are bound to the aromatic ring system Ar, which may be a single ringsuch as benzene and the like, or a plurality of benzene rings linkedtogether directly or by oxygen, carbon, sulfur, phosphorus, alkyl asdefined above, or a fused aromatic ring system such as naphthalene,phenanthrene, and the like.

Suitable substituted phenols include the following:paratertiary-butylphenol, para-secondary-butylphenol,paratertiary-hexylphenol, para isooctylphenol, para phenylphenol,para-benzylphenol, para-cyclohexylphenol, paradecylphenol,para-dodecylphenol, para-tetradecylphenol, para-octadecylphenol, paranonylphenol, para methylphenol, para-beta-naphthylphenol,para-alpha-naphthylphenol, para pentadecylphenol, para cetylphenol,paracumylphenol, para-hydroxy acetophenone, para-hydroxy benzophenone, aphenol alkylated with limonene, a phenol alkylated with oleic acid, aswell as the corresponding ortho and meta derivatives such asmeta-butylphenol and ortho-butylphenol, as Well as mixtures thereof.

Other hydroxyl aromatics which may be used in preparing the compositionsof the instant invention are phenolaldehyde condensation products whichare fusible and soluble such as novolaks or resoles, bisphenols,resorcinol, catechol, hydroquinone, phloroglucinol,polyhydroxynaphthalenes and such compounds containing substituents suchas defined for the substituents on the aromatic ring hereinbefore.Novolak refers to a compound formed by the condensation of a phenol withan aldehyde in the presence of a catalyst and an acid, while a resolerefers to the reaction between a phenol and an aldehyde in the presenceof a base. The novolak is prepared by reacting about 0.5 to 1 mole ofaldehyde per mole of phenol, while a resole requires more than one moleof aldehyde per mole of phenol.

Illustrative bisphenols include:

Typical compounds prepared by this invention are as follows:

where R is:

and the like. The group R may be the same as or different from the acylgroup on the substituent R when R contains an acyl group.

Compounds such as OH OH -Q can be further reacted to produce thebisphenols and derivatives thereof, such as in h OR wherein R is asdescribed above.

In accordance with the present invention the carboxylic acid derivativesof the aromatic derivatives of decachloropentacyclo(5.3.0.0 .0 0decane-S-one can be prepared. A temperature from about 75 degreescentigrade to about 200 degrees centigrade is employed, and a catalystmay or may not be utilized in the preparation of these derivatives.Further, any convenient pressure which includes atmospheric,subatmospheric or super-atmospheric may be employed.

The carboxylic compound employed herein refers to a mono orpolycarboxylic compound which can either be saturated or unsaturated.Such compounds include the acids, acid halides and acid esters, whereinthe acid is of 1 to about 10 carbon atoms. Examples of the monocarboxylic compounds are acetic, propionic, benzoic, toluic, acrylic,methacrylic and the like. Suitable unsaturated polycarboxylic acids andthe corresponding acid halides, esters, anhydrides, and acid esters caninclude maleic, chloromaleic, ethylmaleic, itaconic, citraconic,zeronic, pyrocinchoninic and acetylene dicarboxylic, either alone or inmixtures.

The saturated polycarboxylic compounds useful in the invention can bealiphatic, cycloaliphatic, aromatic or heterocyclic of 2 to about 10carbon atoms. Illustrative of these polycarboxylic acids, acid halides,acid anhydrides and acid esters include phtha'lic, isophthalic,terephthalic, tetrachlorophthali'c, adipic, succinic, 3,4,'5,7,7-hexachloro(1.2.2)bicycloheptene 1,2 dicarboxylic acid ('Het Acid) andmixtures thereof.

The following specific examples further illustrate the invention.However, this detailed disclosure is not to be construed as limiting thescope of the present invention.

EXAMPLE 1 Preparation of the a-isomer of 3-hydroxy-3-(hydroxyphenyl)decachloropentacyclo(5.3.(1.0 .0 -l.0 )dec- (C16H6C110O) In athree-necked flask there was placed 92.1 grams ofdecachloropentacyclo(5.300 .0 decane 3- one, 20.0 grams of phosphoruspentoxide, and 70.5 grams of phenol. The'mixture was heated at 100degrees centi-T grade which resulted in a fluid translucentmass whichwas then cooled to 70 degrees centigrade and HCl gas was passed withgood agitation. The exothermic reaction carried the temperature up to 90degrees centigrade, and the reaction mixture gradually solidified. Heatwas applied to maintain the temperature at 90 degrees centigrade and thereaction was allowed to proceed for three hours. It became too solid tostir, was steam distilled, and the crystalline material that was presentin the distillant was filtered off. A portion of this material wasrecrystallized from aqueous methanol, then from toluene. The finalproduct was a white crystalline material of melting point 266.5-268.5degrees centigrade (uncorrected) and contained 60.5 percent chlorine.Calculated chlorine content for C H CI O is 60.63 percent. The productwas established to be the a-isomer of3-hydroxy-3-(hydroxyphenyl)-decachloropentacyclo(5.3.O.0 .0 .0 decane.

EXAMPLE 2 Conversion of the u-isomer of 3-hydroxy-3-(hydroxyphenyl)decachloropentacyclo(5.3.O.0 .0 .0 decane t0 the diacetate (C I-I Cl OTwo grams of the a-isomer was dissolved in ml. of pyridine and '9 ml. ofacetic anhydride was added slowly. The reaction mixture was refluxed for1 hour, cooled to 0 degrees centigrade and then poured into ice waterand the resulting precipitate was removed on a filter and dried (m.p.164 degrees centigrade uncorrected). The dried precipitate was washed atreflux with methanol and dried (m.p. 169-170 degrees centigradeuncorrected). After a recrystallization from alcohol, a whitecrystalline product was obtained which had a melting point of 170-1715degrees centigrade and was found to contain 52.7 percent chlorine. Thecalculated chlorine content for the diacetate of the a-isomer (C H Cl Ois 53.0 percent. The product was established to be the diacetate of thea-isomer of 3 hydroxy-3-(hydroxyphenyl)-decachloropentacyclo (5 .3.0.0.0 .0 decane.

The compound resulting from the above reaction is suitable for use as afire-retardant additive in plastic materials.

6 EXAMPLE 3 Preparation of the monomethacrylate of the iz-isomer of 3hydroxy 3(hydroxyphenyl-decachloropentacyclo- (5.3.0.0 .0 .0 )decanei-isomer- (87.5 grams) was dissolved in 200 milliliters of pyridine witha slight evolution of heat. Methacrylyl chloride (47.1 grams) was addeddropwise causing a white solid to precipitate due to an exothermicreaction. After the addition of'the acid chloride, the heterogeneousreaction mixture was heated to degrees centigrade, and allowed to coolto 90 degrees centigrade at which temperature it was maintained for 1.5hours. After standing over the weekend, one liter of 10 percent HCl wasadded and the solid material was removed on a filter and washed withwater. After drying, the-product was extracted with benzene, the benzenelayer was washed with water, decolorized with carbon, and concentrated..The crystalline material was removed on a filter and recrystallizedfrom benzene. The final product had a melting point of222-223 degreescentigrade (uncorrected) and was found to contain 54.2 percent chlorine.The chlorine content calculated for the monomethacrylate of the aisomer(C I-I O Cl is 54.3 percent. The product was established to be themonomethacrylate of the u-isomer of 3 hydroxy3(hydroxyphenyl)-decachloropentacyclo (5.3.0.0 .0 .0 )decane. p

The resulting unsaturated ester produced in this example is readilytransformed to a plastic material by the addition of a free radicalgenerating catalyst such as benzoyl peroxides, etc. i

EXAMPLE 4 .1

Preparation of the ,8 isomer c,,H,o1,,o or 3 hydroxy 3(hydroxy phenyl)decachloropentacyclo- 5.3.0 .0 .0 )decane In a three-necked flask therewas placed 118.5 grams of the hydrate of decachloropentacyclo-(5.3.0.O.0 .0 decane-3-one and 49.0 grams of phenol and heated to degreescentigrade to elfect solution. The solution was cooled to 86 degrees and35.0 grams of AlCl were added slowly in small portions. The reactionmixture slowly turned to a deep blue hard mass. Water (one liter) wasslowly added to the reaction mixture, and a blue gray powder resulted.After the addition of water, 200 milliliters of concentrated HCl wasadded. Some evolution of gas took place and a slate gray precipitateresulted, which was washed free of acid with water. After drying, therewas obtained 123 grams of product melting 222- 229 degrees centigrade.

Recrystallization from 75 percent aqueous methanol, followed by arecrystallization from methanol afforded a product which had a meltingpoint of 249-250 degrees centigrade (uncorrected) and a chlorine contentof 61.2 percent. The calculated for formula weight for is 58418 and thechlorine content 60.6 percent. The product was established to be thefi-isomer of 3-hydroxy-3 (hydroxy phenyl) decachloropentacyclo(5.3.0.0.0 .0 decane.

EXAMPLE 5 Conversion of the B-isomer of Example 4 to the diacetate (C HCl O The quantities of reagents and procedure for the preparation of thediacetate of the p-isomer were identical to those used for the a-isomerdescribed above. The diacetate of the p-isomer is a crystalline productwhich melted at 233.0233.5 degrees centigrade (uncorrected) andcontained 53.2 percent chlorine. Calculated chlorine content for C H ClO is 53.0 percent.

7 EXAMPLE 6 Preparation of the dimethacrylate of the p-isomer ofB-hydroxy 3 (hydroxyphenyl) decachloropentacyclo(5.3.0.0 .0 .0 )decaneThe quantities of the reagents and the procedure used for thepreparation of the dimethacrylate of the B-isomer was the same as thatused for the preparation of the monomethacrylate of the a-isomerdescribed above. In the final Work-up the dimethacrylate of thefl-isomer was recrystallized twice from benzene-heptane and finallybenzene. The crystalline product thus obtained melted at 199-200 degreescentigrade (uncorrected) and the melt rapidly polymerized to a gel atthe melting point. It was found to contain 49.5 percent chlorine. Thecalculated chlorine content for the dimethacrylate of the ,B-isomerwherein z is an integer of 1 to 6 and Ar is selected from the groupconsisting of phenyl, naphthyl, and substituted aryl of from 6 to 24carbon atoms, wherein said aryl nucleus is phenyl or naphthyl and saidsubstituents are independently selected from the group consisting of:

(a) alkyl of 1 to 18 carbon atoms;

(b) cyclohexyl or cyclopentyl;

(c) aralkyl of 7 to 18 carbon atoms; and

(d) a halogen independently selected from the group consisting offluorine, chlorine or bromine.

2. The compound of claim 1 wherein z is 1.

3. The compound of claim 1 wherein z is 3.

4. The compound of claim 1 which is the alpha isomer of 3-hydroxy 3(hydroxyphenyl)-decachloropentacyclo (5.3.0.0 '.0 .0 )decaue.

5. The compound of claim 1 which is the beta isomer of 3-hydroxy 3(hydroxypheuyl)-decachloropentacyclo (5.3.0.0 .0 .0 )decane.

6. The compound of claim 1 wherein Ar is substituted phenyl, wherein thesubstituent is aralkyl of 7 to 18 carbon atoms.

References Cited UNITED STATES PATENTS 5/1965 Ellingboe 260-6l9 R 9/1964England 2606l9 R US. Cl. X.R.

260-89.5 H, 486 H, 488 CD, 520, 590, 592, 613 R, 619 F, 620, 860, Dig.24

